Polymer-Plastics Technology and Engineering, 46: 461468, 2007

Copyright # Taylor & Francis Group, LLC

ISSN: 0360-2559 print/1525-6111 online
DOI: 10.1080/03602550701247454

Effects of Plasticizers and Stabilizers on Thermal Stability

of Polyvinyl Fluoride
Jing Wang, Yafei Lu, and Huilin Yuan
The Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials,
Beijing University of Chemical Technology, Beijing, P.R. China

The study was focused on the choosing of plasticizers and

stabilizers for improving thermal stability of polyvinyl fluoride
(PVF) during the thermoplastic processing. Five kinds of organic
esters as plasticizers for PVF were evaluated. The results showed
that dimethyl phthalate (DMP) had better compatibility with
PVF and phase separation didnt occur up to a relatively high
concentration level, and DMP significantly decreased the melting
temperature of PVF and showed the good plasticized effect. The
optimum DMP content, considering homogeneous compound, good
melt fluidity, and dynamic thermal stabilization, can be determined
from the melt flow index and torque measurements. Five kinds of
additives as stabilizers for PVF/DMP system were evaluated by
the color change during static ageing. It was found that pentaerythritol had remarkably positive effects on both thermal and color
stability of PVF.
Keywords Plasticizer; Polyvinyl fluoride; Processing; Stabilizer;
Thermal stability

1. INTRODUCTION
It is well known that blow extrusion is one of the most
frequently used technologies for the production of polymer
films. For polyvinyl fluoride films, similarly, the processing
technology of melt blowing seems to be more desirable
than that of casting relying on organic solutions. However,
up to now, blow extrusion is still impossible for PVF
because of its low thermal stability, which results in its
melting accompanied by partial decomposition of the polymer in thermoplastic processing[13]. Especially, when
undergoing elevated temperatures for a longer time, even
below its decomposition temperature, PVF loses hydrogen
fluoride (HF) and becomes discolored, leading to deleterious changes in the chemical and physical properties of the
polymer[4,5].
Products of the Diamond Shamrock Corporation, the
DALVOR X-6500 series of resins[6,7], represented the only
Address correspondence to Huilin Yuan, The Key Laboratory
of Beijing City on Preparation and Processing of Novel Polymer
Materials, Beijing University of Chemical Technology, Beijing
100029, P.R. China; E-mail: wjdpwjdp@126.com

kind of PVF that can be easily fabricated by melt-blowing

technology, but the feasibility was based on modification
of PVF and detailed technical data has never been
reported. Therefore, an increase in thermal stability of melt
during thermoplastic processing of PVF is an essential
aspect, which can positively influence the blowing technology of PVF films. Some research articles[5,810] have
dedicated to studying the thermal and oxidative degradation of PVF, and a few of patents[1114] were focused on thermal stabilizers for preventing the discoloration and
degradation of PVF, but those inventions were particularly
applicable to the stabilization of coatings and casting films
of PVF or pigmented vinyl fluoride polymer systems. In
addition, the plasticization of PVF with the use of dibutyl
phthalate and tricresyl phosphate, for avoiding thermal
decomposition, was also been mentioned[3]. Whether those
effects will ever be sufficient to overcome, entirely, the
problem of thermal decomposition of PVF during thermoplastic processing and ensure the success of melt-flowing of
PVF without significant drop in physical properties,
further investigation will be required.
To develop the melt-blowing technology for PVF films
by conventional extruder without modification, the aim
of this study is to improve the thermal and processing stability of PVF in thermoplastic processing. Different kinds of
plasticizers and stabilizers were compared and analyzed
and their optimum contents were determined in this article.
In addition, the investigations on the thermal and color
stability of PVF were also reported when DMP and
pentaerythritol were used together.
2. EXPERIMENTAL
2.1. Materials and Chemical Agents
PVF-J328 (white powder) used in all experiments was
supplied by Zhejiang Lantian Environmental Protection
Material Co., Ltd. (China). This resin had a viscosity
average molecular weight of 3.86
105 with a melting
point of 195C. The characteristics of the five plasticizers

461

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JING WANG ET AL.

TABLE 1
The characteristics of plasticizers used and the melting temperatures of plasticized PVF
Characteristics

Plasticizers

Molecular structures

Boiling
Solubility
point=C parameter[15,20]
(101.3 kPa) d=(cal=cm3)1=2

Melting
temperatures of
plasticized PVF=C

Dimethyl phthalate
(DMP)

282

10.45

138.4

Dibutyl phthalate
(DBP)

339

9.30

171.9

Dioctyl phthalate
(DOP)

284

8.80

186.4

Trioctyl
trimellitate
(TOTM)

370

8.86

189.8

Dioctyl sebacate
(DOS)

248

8.34

191.6

Note: Solubility parameter of PVF 12.20 (cal=cm3)1=2.

(99.5% purity), dimethyl phthalate (DMP), dibutyl

phthalate (DBP), dioctyl phthalate (DOP), trioctyl trimellitate (TOTM), and dioctyl sebacate (DOS), and five
stabilizers (98% purity), sodium formate, polyvinylpyridine, pentaerythritol, sodium salicylate, and di-n-butyltin
dilaurate, used in this study are listed in Tables 1 and 2,
respectively.

TABLE 2
Stabilizers used and their contents
Stabilizers
Pentaerythritol
Di-n-butyltin dilaurate
Sodium formate
Polyvinylpyridine (K30)
Sodium salicylate
1

Additive content=phr1
1.0
1.0
1.0
1.0
0.5

2.0
2.0
2.0
2.0
1.0

3.0
3.0
3.0
3.0
2.0

phr parts per hundreds of resin (or rubber)

4.0

2.2. DSC Measuremensts

Differential scanning calorimetry (DSC) analysis for
plasticized PVF was performed from 30250C at a rate
10C=min under nitrogen atmosphere by the model STA449C thermal analyzer (NETZSCH Company). The plasticizer content in the samples for DSC test was 100 phr (all
concentrations were based on 100 g PVF).
2.3. MFI and Compatibility Measurements
According to ASTM-D1238 standard, the melt flow
index (MFI) of the mixtures of PVF and different plasticizers were measured using a Melt Indexer (XNR-400). The
test temperatures were 210, 220, and 230  0.2C, respectively, and the loading weight was 10.0 kg.
Visual observation described in the book[15] was used to
estimate the compatibility between PVF and plasticizers.
To cool the threads extruded from the capillary of Melt
Indexer in a closed container from 220C to the room
temperature, then observe carefully their transparency

463

EFFECTS ON THERMAL STABILITY OF POLYVINYL FLUORIDE

and flexibility and wipe the extrudates with bibulous

papers and observe whether the excessive plasticizer will
exude to the surface of extrudates due to phase separation.
If the extrudate is transparent and flexible, and furthermore, the bibulous is not greased, it can be concluded that
the compatibility of PVF=plasticizer is good.

compatibility and plasticized effects of plasticizers on

PVF. Table 1 listed the characteristics of five kinds of plasticizers we used. These plasticizers were either repeatedly
mentioned in some published papers[3,17,18] or have been
used as effective plasticizers in vinyl-type resin such as
polyvinyl chloride.

2.4. Torch Measurements

Torque Rheometer (Thermo Haake Type 557-1302) was
used for torque recording during PVF=DMP melt kneading at the temperature of 220C and rotor speed of 80 rpm.

3.1.2. The Compatibility Between Different

Plasticizers and PVF
For a plasticizer to be compatible with a polymer, it is
generally considered that the two must have similar solubility parameters (d). Plasticizer-polymer compatibility is
good if the two d values do not differ by more than
about  2.045 (cal=cm3)1=2[15]. The d values of PVF and
five kinds of plasticizers are listed in Table 1. As can
be seen that d value of PVF is 12.20 (cal=cm3) 1=2[19].
According to the theory of solubility parameters, the
relative compatibility can be obtained from Table 1 starting from the most compatible plasticizer in the order of
DMP < DBP < DOP,TOTM < DOS. Here only DMP
has a d value of 10.45 (cal=cm3)1=2 within the required
range and was regarded as the best compatible plasticizer,
whereas the others have only limited compatibility
with PVF.
Visual observation was also carried out to define the
best suitable plasticizer, which would give the maximum
compatibility with PVF resin and form a homogeneous
mixture under normal processing condition and the plasticizer wont separate from the compound on cooling.
Table 3 shows the compatibility results of different
PVF=plasticizer systems. When the contents of DMP varied from 60120 phr and that of DBP was 100 phr, the
extrudates looked transparent, homogeneous, and flexible.
It meant that the phase separation didnt occur. For DOP
and TOTM, the extrudates can keep homogeneous only
when their contents were below 60 phr, but they were opaque and inflexible. DOS was hardly compatible with PVF.
All these phenomena were fully consistent with the results
estimated by solubility parameters.

2.5. Static Ageing and Color Change Tests

The static ageing tests of PVF=DMP (100=100) mixtures
in the absence or presence of stabilizers were performed in a
ventilated heat oven at 220C according to ISO 305-1990=B
standard. In the course of operation, safety precautions
must be taken against hydrogen fluoride (HF) given out
due to extensive degradation of PVF. Then using a
Datacolor International Dataflash100 Spectrophotometer,
the color changes in surface of the aged samples compared
with the unaged samples were measured according to ISO
7724=1 standard. Five different points in each sample were
measured, averages were obtained, and in this way the total
differences in color, dE, of the tested samples were
recorded. It is generally considered that the lower the dE
value is, the slighter the degradation is, and the more effective the stabilizer is.
2.6. TG and DTG Measurements
Thermogravimetric (TG) and differential thermogravimetric (DTG) curves were recorded with a model of
STA-449C Thermal Analyser (NETZSCH Company).
The samples were heated in nitrogen atmosphere within
temperature ranges of 25500C and a heating rate of
10C=min. The DMP content in the samples for TG and
DTG tests was 100 phr.
3. RESULTS AND DISCUSSION
3.1. Effects of Plasticizers on Thermal Stability of PVF
3.1.1. The Choosing of Plasticizers
Usually, PVF must be plasticized before extrusion processing. After adding plasticizer to PVF, the melt point
and viscosity of PVF can be declined which partly avoids
thermal degradation of PVF during melting and extrusion
processing. So the choosing of plasticizer for PVF becomes
a critical issue to be solved. The first requirement of a plasticizer is that it must be compatible with polymer; that is,
the liquid plasticizer must blend uniformly with the solid
polymer, and the compound can remain homogeneous
when cooled to room temperature and throughout the
useful life of the plastic product[16]. However, there has
been little work toward studying the PVF-plasticizer

TABLE 3
Compatibility measurement of PVF=plasticizer systems
at 220C
Compatibility
Plasticizers 20 phr 40 phr 60 phr 80 phr 100 phr 120 phr
DMP
DBP
DOP
TOTM
DOS

O,H,I
O,H,I
O,H,I
O,H,I
O,H,I

O,H,I
O,H,I
O,H,I
O,H,I
O,PS

T,H,F
O,H,I
O,PS
O,PS

T,H,F T,H,F T,H,F

O,H,F T,H,F T,PS,F
O,PS

O,PS

Code: O opaque; T transparent; H homogeneous;

PS phase separation; F flexible; I inflexible.

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JING WANG ET AL.

Combining the molecular structural formulas of

plasticizers in Table 1, it can be found, for PVF resin aromatic plasticizers had better compatibility than aliphatic
plasticizers, and the compatibility varied from good to
bad with the increasing carbon atoms of alkyl of aromatic
plasticizers[15]. The reason is that for polar polymers such
as PVF, short-chain aromatic ester such as DMP and
DBP[20] have higher polarity, stronger solvating power
and smaller diffusant dimension than long-chain fatty
esters such as DOS, and so provide better compatibility
with PVF[16].
3.1.3. Plasticized Effects of Plasticizers on PVF
There are many factors, which are likely to influence
plasticized effects of plasticizer on PVF resin, but the most
important one is the compatibility[15]. In order to further
understand the correlation between plasticized effects and
compatibility, the DSC heating thermograms of plasticized
PVF and pure PVF are shown in Fig. 1. It can be seen that
the melting peak temperatures of all the plasticized PVF
were reduced compared with that of pure PVF, but the
diminished magnitude were very different even though
the same contents of plasticizers. From the data in
Table 1, the melting temperature (138.4C) of the PVF
plasticized with DMP was lower about 57C than the melting point (195C) of the pure PVF. With regard to DBP,
the decrease of the melting temperature of plasticized
PVF was also obvious, but the variation was very little
for PVF plasticized with DOP, TOTM or DOS. The results
indicated that the better the compatibility between plasticizer and PVF was, the more obvious the plasticized effect
was. The reason is that only those plasticizers, which are
compatible with PVF can diffuse and insert between
PVF molecules to the utmost extent, and consequently

FIG. 1. DSC heating thermograms of plasticized PVF and pure PVF.

destroy many of those points of attachment along the

polymer chains by replacing PVF-PVF interactions with
PVF-plasticizer interactions[21].
Besides the excellent compatibility and plasticized
effects, as can be seen from Table 1, the boiling point
(282C) of DMP is far higher than the melting temperature
of plasticized PVF with it, and therefore DMP is considered as the optimal plasticizer for PVF in this work.
3.1.4. The Effects of the Kinds and Concentration of
Plasticizer on Melt Fluidity of PVF
In order to compare the performance of different kinds
and concentrations of plasticizers in improving melt fluidity of PVF, the MFI of the mixtures of PVF=DMP and
PVF=DBP were tested at 220C with varied plasticizer contents from 40120 phr. As can be seen from MFI curves in
Fig. 2, the MFI of PVF=DMP was remarkably raised with
increasing DMP content, especially beyond 80 phr. However the MFI of PVF=DBP almost kept invariable when
the DBP content is beyond 90 phr. At 120 phr, the MFI
of PVF=DMP is four times than that of PVF=DBP. From
the experimental results, the better the PVF=plasticizer
compatibility and the higher the plasticizer concentration,
better is the melt fluidity. It is reasoned that since the major
force resisting deformation of PVF is intermolecular friction, the plasticizer, which can really diffuse into intermolecular in large amount would separate the PVF chains and
facilitate their movement over each other.
The dependence of the melt fluidity of PVF on temperature in the presence of 100 phr DMP is shown in Fig. 3. It
showed that the MFI curve at 220C was wholly over the

FIG. 2. MI of PVF=DMP and PVF=DBP mixtures as a function of

plasticizer content at 220C.

EFFECTS ON THERMAL STABILITY OF POLYVINYL FLUORIDE

465

FIG. 4. Variation of torque with kneading time for PVF=DMP mixtures

at 220C.
FIG. 3. MI of PVF=DMP mixtures as a function of DMP content at
different temperatures.

MFI curves at 210 and 230C and the MFI values at 220C
were highly sensitive to the DMP concentration. It means,
though the increasing temperature can usually lead to a
decreasing melt viscosity and better melt fluidity, the
excessively high temperature may result in a partial volatilization of DMP and a partial degradation of PVF.
3.1.5. The Torque Analysis of PVF=DMP System
In the case of long-time thermal and mechanical loading, the degradation and ageing reactions occur in PVF
melt. It preferentially induces the increase of melt viscosity
of PVF due to ageing. Therefore, the starting time of the
thermal stability deterioration of PVF=DMP system can
be defined as the increase of torque and in this way to
determine the concentration of DMP, which is fit for the
thermoplastic processing of PVF.
In order to verify the stabilization of DMP to PVF, pure
PVF resin was firstly placed in Haake torque rheometer at
the constant temperature of 220C and speed of 80 rpm.
The curves exhibited in Fig. 4 showed that pure PVF
underwent the molten state accompanied by severe ageing
and the torque increased sharply from 0.310.6 Nm, and
then degraded completely in about 3 min and the torque
decreased sharply from 10.60.8 Nm due to the molecular
chains breaking down drastically. However, when the prepared mechanical mixture (60 g) of PVF with DMP was
placed in the Rheometer at the same conditions for
20 min and the torque was continually recorded during
kneading, it can be found in Fig. 4 that DMP really
retarded the ageing and degradation of PVF. By contrasting the torque records of four PVF=DMP samples with the
different DMP contents, we can also find the torque values

gradually decreased with increasing DMP contents.

However, the torque values started to increase about
6 min later when DMP content was 60 and 80 phr but they
can almost keep unchanged up to 20 min when the content
is beyond 100 phr. It indicates that the PVF=DMP system
has longer dynamic thermal-stability time when DMP content is up to 100 phr, which gives the absolute permission to
the thermoplastic processing of PVF. In addition, it was
noticeable that MFI values of the blends with 100 and
120 phr DMP at 220C were largely different in Fig. 3,

FIG. 5. Color changes of PVF=DMP samples subjected to heat treatment at 220C in a ventilated heat oven.

466

JING WANG ET AL.

FIG. 6. Discoloration curves of PVF=DMP mixtures containing different kinds of stabilizers (a) pentaerythritol; (b) di-n-butyltin dilaurate; (c) sodium
formate; (d) polyvinylpyridine; and (e) sodium salicylate.

but their torque curves were almost superimposed. This

disagreement may result from the heavier volatilization of
DMP caused by shear and friction heat buildup in Haake
torque rheometer than in melt indexer [21].

3.2. Effects of Stabilizers on Thermal Stability of PVF

3.2.1. The Choosing of Stabilizers
At the high temperature and long-time processing
conditions, PVF=DMP samples will take on a series of

EFFECTS ON THERMAL STABILITY OF POLYVINYL FLUORIDE

FIG. 7. Discoloration curves of PVF=DMP compounds in the presence

of five kinds of stabilizers at the optimum content.

characteristic colors, as shown in Fig. 5, from transparency ! light yellow ! yellow ! orange yellow ! orange
red ! red ! dark brown ! dark. For example, during the
torque measurements the compound of PVF with 100 phr
of DMP appeared light yellow after 20 min even though
it could still keep low melt viscosity.
In order to further improve heat stability of PVF and
provide an increased resistance to color deterioration in
the thermoplastic processing, five additives as stabilizers
had been tried to use for PVF=DMP system. It is well
known that color protection is an important criterion of
stabilizer effectiveness and so the color change, dE, as the
most direct evidence of PVF degradation was employed
to indicate whether those stabilizers are effective or not.
Fig. 6 showed the discoloration curves of PVF=DMP in
the absence and presence of stabilizers. A very similar trend
was found that the presence of each stabilizer could retard
the development of discoloration, but the dE values of
samples with varied stabilizer kinds and contents were very
different. The contents of stabilizers used were listed in
Table 2 within a range from 04 phr. The results shown
in Fig. 6a and 6b exhibited that the best effects (the lowest
dE values) were obtained when 2 phr of pentaerythritol or
di-n-butyltin dilaurate, respectively were added into
PVF=DMP system. In Fig. 6c and 6d, when the contents
of sodium formate and polyvinylpyridine were 4 and
3 phr, respectively, the decrease of dE was the most
obvious. In Fig. 6e, however, the influence of the content
on dE was very little, and so 1 phr of sodium salicylate
was chosen for the following investigation.
Comparing the lowest dE values of the above five stabilizers whose corresponding optimum contents had been
obtained from Fig. 6, it can be found in Fig. 7 that 2 phr

467

FIG. 8. TG and DTG curves for PVF=DMP in the absence and

presence of pentaerythritol.

of pentaerythritol when used provided adequate protection

to PVF=DMP system against color deterioration. With
regard to the stabilizing mechanism of pentaerythritol as
a stabilizer for PVF=DMP system will be investigated
further in our forthcoming study.
3.2.2. TG and DTG Analysis
The thermal degradation of PVF plasticized with 100 phr
of DMP in the absence and presence of pentaerythritol was
investigated using TG and DTG analysis. The typical
thermogravimetric curves obtained are shown in Fig. 8.
The thermal degradation of PVF=DMP shows a two-step
process. The first step (up to 200C) mainly involves
volatilization of DMP and the second step (up to 550C)
concerns the degradation of PVF. We can see that the
addition of pentaerythritol led to a small delay in the evaporation of DMP, and the value of Tmax (the temperature of
DMP at maximum weight loss) for the pentaerythritol
system was higher than that of another system. This experimental feature indicated the stabilizing effects of DMP and
pentaerythritol were synergistic in the case of appropriate
contents.
4. CONCLUSIONS
From the experimental results of compatibility, DSC,
MFI, torque, and dE measurements, DMP and pentaerythritol were picked out and used together for the thermoplastic processing of PVF. DMP as an effective
plasticizer shows excellent compatibility with PVF. It has
an appreciable role in decreasing melting temperature
and enhancing melt fluidity and processing stabilization
of PVF. Pentaerythritol as a suitable stabilizer retards
effectively the development of discoloration of PVF=DMP

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JING WANG ET AL.

system and improves the thermal stabilization of PVF during thermoplastic processing.
ACKNOWLEDGEMENTS
The authors wish to thank Zhejiang Lantian Environmental Protection Material Co., Ltd. China for supplying
with PVF resins through project.
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